Abstract

The heat capacity of synthetic eskolaite, Cr2O3, and of the synthetic spinels magnesiochromite, MgCr2O4, and chromite, FeCr2O4 were measured from 1.5 K to 340 K. For MgCr2O4, a substantial magnetic contribution to the entropy is revealed by a sharp peak in the heat capacity curve at 12.55 ± 0.05 K, which indicates the transition to antiferromagnetic long-range order. Integration of the heat capacity curve yields a value of 118.3 ± 1.2 J/(mol·K) for the standard entropy at 298.15 K, which is in excellent agreement with that calculated from phase equilibria studies on the reaction MgCr2O4 + SiO2 = Cr2O3 + MgSiO3. The new calorimetric results for Cr2O3 indicate a standard entropy at 298.15 K of 82.8 ± 0.8 J/(mol·K). The measurements for FeCr2O4 show three distinct heat capacity anomalies, one of which (peaking at 36.5 ± 0.2 K) was missed by previous low temperature heat capacity measurements, which only extend down to 53 K. Integration of the heat capacity curve yields a value for the standard entropy at 298.15 K of 152.2 ± 3.0 J/(mol·K) for FeCr2O4, some 6 J/(mol·K) greater than the previous calorimetric value.

These low-temperature heat capacity data were combined with high-temperature heat content measurements from the literature to derive heat capacity equations for all three phases to 1800 K. The resulting heat capacity equations were then used to extract revised recommended values of the standard enthalpies of formation and entropies of MgCr2O4 and Cr2O3 from phase equilibrium data. For FeCr2O4, the phase equilibrium data are of dubious accuracy, the enthalpy of formation is only approximate.

You do not currently have access to this article.